Composites of Aluminum Oxide and Cerium/Zirconium Mixed Oxides

ABSTRACT

The subject matter of the invention is a method for producing composites comprising aluminum oxide and cerium/zirconium mixed oxides, hereinafter referred to briefly as Al/Ce/Zr oxide composite(s) using boehmite and soluble cerium/zirconium salts. Al/Ce/Zr oxide composites produced in this way have an increased thermal stability.

The present invention relates to a method for producing compositescomprising aluminum oxide and cerium/zirconium mixed oxides, hereinafterreferred to in abbreviated form as Al/Ce/Zr oxide composite(s). Al/Ce/Zroxide composites produced in this way have an increased thermalstability.

Al/Ce/Zr oxide composites with incorporated catalytically active noblemetals are known and are used for catalytic exhaust gas aftertreatment,for example, of combustion gases in particular, which have beendischarged from the combustion chamber(s) of motor vehicles. Suchautomotive catalysts usually consist of multiple components. A thermallystable honeycomb body made of ceramic, usually cordierite, or metalfilms having a plurality of thin-walled channels is used as the carrier.The so-called wash coat, comprising porous aluminum oxide (Al₂O₃) andoxygen storage components, is applied to the carrier. The wash coat alsocontains catalytically active noble metals incorporated into it. Inmodern exhaust gas catalysts, these are platinum, rhodium and/orpalladium. The ceramic carrier is supported in a metallic housing withthe help of special bearing mats made of high-temperature wool, forexample, less often in combination with wire mesh. Wash coats containingAl/Ce/Zr oxide composites are known for aftertreatment of exhaust gas ofcombustion engines in which the cerium/zirconium mixed oxides act asoxygen storage components. The Al/Ce/Zr oxide composites according tothis invention are used in the above automotive catalysts.

WO 2006/070201 A2 describes an improved variant for producing mixedoxides of aluminum oxide, zirconium oxide and optionally at least onerepresentative from CeO₂, La₂O₃, Nd₂O₃, Pr₆O₁₁, Sm₂O₃, Y₂O₃ and possiblyother rare earth oxides. Production is based on joint precipitation ofthe corresponding salts. The mixed oxides are produced by jointprecipitation of all the oxides involved, starting from a metal saltsolution, where the pH is adjusted in the range of 8.5±1 duringprecipitation. Precipitation is performed by adding alkali hydroxides,in particular sodium hydroxide solution.

WO 2008/113457 A1 describes the production of Al/Ce/Zr oxide compositesbased on mixtures of aluminum oxide and cerium/zirconium mixed oxidesthat are produced separately.

U.S. Pat. No. 5,883,037 describes the importance of the thermalstability of the composite materials. The process described here is amultistep process, in which Ce, Zr and optionally Pr salts are firstprecipitated by raising the pH and then the precipitate is isolated. Theprecipitate is brought into contact with alumina while mixing, thenisolated and subjected to drying and calcination. The alumina ispreferably stabilized by foreign ions from the group of rare earths, Ba,Zr or Si. The Ce/Zr mixed oxides and Ce/Zr/Pr mixed oxides produced byprecipitation may optionally also be stabilized, e.g., by at least oneelement of group VIII, bismuth or some other rare earth element. Onedisadvantage of this production process is due to the low homogeneity ofthe resulting material.

EP 1172139 A1 describes the production of homogeneousAl₂O₃/CeO₂/ZrO₂/Y₂O₃/La₂O₃ mixed oxides by coprecipitation as well astheir thermal stabilities. In the process described there, theAl—Ce—Zr—Y—La hydroxide intermediates resulting from joint precipitationwere calcined and thus converted to the oxides.

WO 2006/119549 A1 describes a process in which a solution of metal saltsis added to an acidic boehmite suspension to obtain a second suspension.Precipitation is induced by dropwise addition of the second suspensionto an alkaline solution. The method of WO 2006/119549 A1, as also shownby Examples 1 and 2, leads to the development of discrete islands ofCe/Zr/rare earth mixed oxide in addition to aluminum oxide. A verysimilar process is described in Comparative Examples 3, 14 and 15 ofU.S. Pat. No. 6,831,036. The residual surface areas described there aremax. 39 m²/g after calcination at 1000° C. for three hours due to theprocess.

WO 2012/67654 A1 describes a process in which Al/Ce/Zr/rare earth oxidecomposite is produced by a two-step precipitation. In the first stephere an “aluminum hydrate” and optionally a rare earth hydroxide areproduced by precipitation of aluminum sulfate with sodium aluminate.After renewed acidification of the suspension, then the Ce/Zr/rare earthcomponent is precipitated by adding the corresponding salt solution tothis suspension and then increasing the pH again. The Al/Ce/Zr/rareearth oxide composite thereby obtained should have a surface area (inm²/g) that can be obtained from the formula SA=0.8235·[Al]+11.157 aftercalcining at 1100° C. for five hours. The residual surface area of thematerials after calcining at 1200° C. for five hours is obtained by theformula SA=0.3·[Al]+7. WO 2012/67654 A1 was published subsequently. Therespective priority application relates to a different subject matterthan that indicated above.

The object of the present invention is to provide improved Al/Ce/Zr(optional rare earth) oxide composites having a definitely higherthermal surface stability, in particular at temperatures of 1100° C. ormore (e.g., for 24 hours or more). Surface stability in this senserefers to (largely) preserving the surface at high temperatures asmeasured according to BET. At the same time a maximum degree ofhomogeneity is to be achieved. Homogeneity here is understood to be auniform distribution of the phase of Al₂O₃ and Ce/Zr/rare earth mixedoxide without the formation of discrete islands.

This object is achieved by a method according to claim 1. Preferredembodiments are the subject matter of the dependent claims and/or aredescribed below.

It has been found that the Al/Ce/Zr oxide composites obtained by themethod according to the invention and optionally containing additionalrare earth oxide components at least contain the Ce/Zr oxide in the formof a solid solution. This can be proven by x-ray powder diffractionanalysis. In addition Al₂O₃ and the Ce/Zr (optional rare earth) mixedoxides are present in a completely homogeneous distribution side byside, as has been demonstrated by EDX (energy-dispersive X-ray analysis)and element mapping. No domains for individual metal oxides weredetected. The indication // reporting of the components Al₂O₃ and Ce/Zrmixed oxides and/or Ce/Zr (optional rare earth) mixed oxides and/orAl/Ce/Zr (optional rare earth) oxide composites does not preclude othermetal oxide being components of the mixed oxides or of the composite.The composites preferably consist only of Al₂O₃ and Ce/Zr (optional rareearth) mixed oxides.

The process described in this invention differs from the prior artdescribed above in that an aqueous alkaline boehmite suspension (slurry)is used and the precipitation is performed in the suspension in thepresence of soluble metal salts, forming a Ce/Zr (optional rare earth)hydroxide precipitate wherein the Ce/Zr (optional rare earth) hydroxideprecipitate (unlike the later solid solution) is homogeneouslydistributed in the boehmite matrix. The degree of homogeneity and theeffective separation of the Ce/Zr (optional rare earth) mixed oxidecrystallite by the aluminum oxide which is associated with this isachieved by a very homogeneous precipitation in which the boehmiteparticles do not sediment within the suspension even in an alkalinemedium. The consistently high pH ensures a uniform precipitation of theCe/Zr (optional rare earth) hydroxides so that these are present in theform of a homogeneous solid solution after calcination.

In the process described here the use of alkali and in particular sodiumhydroxide solution may be omitted. Removal of alkali and/or sodiumhydroxide from the composite material is absolutely essentially for theapplication and thus the omission of these components constitutes animportant advantage.

The inventive method comprises the following steps:

-   -   (a) Providing a suspension comprising boehmite as the alumina        precursor and adjusting the pH to 6-11.5, preferably 8 to 10.5        or 9 to 10.5, e.g., with an aqueous solution of ammonia. A        preferred embodiment involves an aqueous suspension of boehmites        which are modified with organic compounds comprising at least        one carboxyl group and one or more additionally groups selected        from hydroxy(—OH), oxo(—O), carboxy(—COO) and/or amine(—NH)        groups, e.g., tartaric acid or citric acid, preferably in        amounts by weight of 0.1% to 50% by weight, in particular 3% to        12% by weight, based on the dry weight of the boehmite.    -   (b) Preparing an aqueous metal salt solution containing metal        salts of cerium and of zirconium and optionally one or more rare        earth elements. All water-soluble salts (e.g., acetates,        nitrates, chlorides) are suitable for this production. Soluble        in this sense means that a stable solution of at least 5 g salt        (based on the oxidic form of the metal) in 100 g water is        established while stirring at the reaction temperature. In a        preferred embodiment, metal nitrates are used. Ammonium        cerium(IV) nitrate, in particular is used as the cerium source.        According to another preferred embodiment, cerium(III) nitrate        may be used if the resulting metal salt solution is oxidized,        e.g., with an aqueous H₂O₂ solution.    -   (c) Bringing the suspension of (a) in contact with the metal        salt solution from (b) preferably at a pH of 6.5 to 11, in        particular 8 to 10.5, especially preferably 8.5 to 10 and        independently thereof, in particular at temperatures of 5 to        95° C. preferably 80 to 95° C. or exposing the resulting slurry        to these temperatures, in particular        -   (c1) Starting with the metal salt solution and adding by            drops the alumina precursor suspension and then adjusting            the pH to 6.5 to 11, in particular 8 to 10.5, especially            preferably 8.5 to 10.        -   (c2) Starting with the metal salt solution and adding by            drops to the alumina precursor suspension while at the same            time adjusting the pH to 6.5 to 11, in particular 8 to 10.5,            especially preferably 8.5 to 10.        -   (c3) Starting with the alumina precursor and simultaneous            dropwise addition of the metal salt solution and the ammonia            solution to obtain a pH of 6.5 to 11, in particular 8 to            10.5, especially preferably 8.5 to 10.    -   (d) Separating the aqueous solution and washing the solids        from (c) with water.        -   (d1) Optionally the suspension from (c) is hydrothermally            aged (autoclaved), then filtered and the solids washed with            deionized water.        -   (d2) Drying the solids from (d), e.g., by        -   (d2.1) Drying the solids, e.g., at 120° C. for sixteen hours            under the influence of heat.        -   (d2.2) Redispersing the solids from (d or d1) and then spray            drying. In a special embodiment, one or more additional            soluble compounds are added before spray drying and in            particular only after step (c) or after redispersing. The            preferred salts are acetates, e.g., La acetate and/or salts            of the alkaline earth elements, rare earth elements,            zirconium or silicon.    -   (e) Calcining the solids from (d or d1 or d2), e.g., in the        temperature range of 550-1200° C. preferably in the range of        600-1000° C., in particular for at least one hour.

To adjust the pH, nitrogen bases may be used, including urea orurotropin, for example, in addition to ammonia. The suspensioncomprising boehmite, in particular is thus adjusted to the required pH.

The composite may also comprise one or more alkaline earthelements/compounds, rare earth elements/compounds, zirconium and/orsilicon, in particular rare earth elements/compounds, wherein these arepreferably added before drying, in particular only after step (c) oreven (d) in the form of one or more additional soluble compounds.

According to one embodiment the suspension of (c) is aged hydrothermallyin an aqueous environment, preferably at a temperature of at least 90°C. for at least one hour, in particular for at least four hours at atemperature of at least 120° C.

In particular water-soluble salts of the metals are used to produce themetal salt solution, e.g., acetates, nitrates and/or chlorides. In theinventive methods, the addition of alkali salts and/or alkaline earthsalts is preferably omitted, excluding barium salts which may optionallybe used.

The Ce/Zr (optional rare earth) oxide is in the form of a solid solutionin the composite, and Al₂O₃ and the Ce/Zr (optional rare earth) mixedoxide/solid solution are present in homogeneous distribution side byside.

The Al/Ce/Zr oxide composite preferably contains 20% to 80% by weightpreferably 40% to 70% by weight aluminum, 5% to 80% by weight preferably5% to 40% by weight zirconium, 5% to 80% by weight preferably 5% to 40%by weight cerium, 0% to 12% by weight preferably 0.1% to 9% by weightrare earth metal(s) (RE), calculated as Al₂O₃, ZrO₂, CeO₂, RE₂O₃. Theamount of the other soluble compounds added in step (d2.2) afterredispersing is preferably 0.1% to 15% by weight (calculated as oxide)based on the weight of Al₂O₃. Preferred rare earth metals includeneodymium, praseodymium, yttrium and/or lanthanum.

The Al/Ce/Zr oxide composites preferably still have a surface area of atleast 20 m²/g preferably at least 40 m²/g after four hours at 1200° C.

The aluminum/cerium/zirconium mixed oxides can be used in automotivecatalysts such as three-way catalysts (TWC) or also in other componentssuch as NO_(x) storage mechanisms, diesel oxidation catalysts (DOC) anddiesel carbon black particle filters (DPF). Their structure wasdescribed in the introduction.

Boehmites in the sense of this invention are compounds of the generalformula AlO(OH)×H₂O. Boehmites produced by hydrolysis of an aluminumalkoxide are preferred; see U.S. Pat. No. 5,055,019 (“Process for theProduction of Boehmitic Aluminas”). By this process, boehmitic aluminasare obtained in a purity of at least 99.95% Al₂O₃ with defined poreradii in a range between 3 and 100 nm by salt-free aqueous neutralaluminum alcoholate hydrolysis, wherein the alumina suspension obtainedfrom aluminum alcoholate hydrolysis is aged in an autoclave a) at awater vapor pressure of 1 to 30 bar corresponding to a temperature of100 to 235° C., b) in a period of 0.5 to 20 hours and c) while stirringat a circumferential velocity of 1.0 to 6.0 m/s.

According to the invention aluminum alcoholates are used in theproduction of the boehmitic aluminas to obtain high purity products. Thealuminum alcoholates may be synthesized by the Ziegler process, forexample, in which a purification step is performed by filtration. Toproduce the aluminum alcoholates, for example, C₁ to C₂₄ alcohols ormixtures thereof may be used, for example.

The boehmites that are used are characterized by their especially highpurity among other things (concentrations of SiO₂≤approx. 0.01%,Fe₂O₃≤approx. 0.01%, Na₂O≤approx. 0.002%, K₂O≤approx. 0.002%,TiO₂≤0.005%, other elements≤0.01%). Regardless of this in anotherpreferred form, boehmites having a pore volume of 0.4 to 1.2 mL/g and/orcrystallite sizes of 4 to 40 nm preferably 4 to 16 nm measured on the(120) reflex are used.

According to an especially preferred embodiment, the boehmites aremodified with organic compounds having at least one carboxy group andone or more additional groups selected from hydroxy(—OH), carboxy(—COO)and/or amine(—NH, including —NH₂) groups, e.g., tartaric acid or citricacid, in particular with 2 to 12 carbon atoms, especially preferably 4to 8 carbon atoms, preferably in amounts by weight of 0.1% to 50% byweight, in particular 5% to 15% by weight, based on the dry weight ofboehmite. These present agglomeration and sedimentation of the boehmitesin the alkaline medium. Other suitable substituted carboxylic acids inthe sense of the invention include 2-hydroxypropionic acid,2-oxopropionic acid, hydroxybutanedicarboxylic acid,dihydroxybutanedicarboxylic acid, 2-hydroxypropane-1,2,3-tricarboxylicacid (citric acid), L-aspartic acid, L-serine, glycine, L-leucine,L-tyrosine or L-tryptophan, for example.

The composites produced according to the invention comprise aluminumoxide and cerium/zirconium (optional rare earth) mixed oxides and haveas catalyst also platinum rhodium and/or palladium according to oneembodiment.

Based on the present invention, it has also been found thatprecipitation in the presence of an alkaline suspension of a boehmitemodified by addition of the above multifunctional organic acids, inparticular in combination with the use of ammonium cerium(IV) nitrate asthe cerium source leads to end products with an especially great thermalstability. Surprisingly and independently thereof, this effect isespecially pronounced when the alkaline suspension is added by drops tothe metal salt solution.

The invention will now be explained in greater detail based on theillustrations, in which

FIG. 1 shows the particle size distributions of Examples A1 and A2 inaqueous suspensions;

FIG. 2 shows x-ray powder diffractograms of the material from Example 2after calcination.

The following experimental examples show that

a) higher residual surface areas are obtained in comparison with thesynthesis procedures in EP 1172139 B1 and WO 2012/067654 A1,

b) high residual surface areas are obtained even after calcination underespecially sharp conditions (1150° C./36 h, 1200° C./4 h),

c) in Comparative Example 3, surface areas which are also very high andare within the range of the inventive composites produced by the processdescribed here (Comparative Example 3 and Example 6) are obtained,however, the process described here does not require the use of sodium,which is a significant advantage in the process technology becausesodium leads to poisoning of noble metal catalysts

d) in Comparative Example 5 high residual surface areas were alsoobtained which are also within the range of the composites produced bymeans of the process described here (Comparative Example 5, Examples 7and 8).

However, in one embodiment, the process described here proposes the useof modified boehmite, which facilitates dispersibility in an alkalinemedium. Thus there is no agglomeration or sedimentation of the boehmite,but instead there is an especially homogeneous precipitation anddistribution of the CeO₂/ZrO₂/(optional rare earth oxide) components atan elevated pH in the presence of finally dispersed boehmite, which isapparent on the basis of the particle sizes in the aqueous suspension ata high pH. This is demonstrated in Examples A1 and A2.

The measurements of the surface areas (BET) were performed using aMicromeritics TriStar 3000 according to DIN ISO 9277. The x-raydiffractograms were measured using a Panalytical X′Pert Pro MDBdiffractometer. The percentage amounts are percent by weight, unlessotherwise indicated. The particle distributions were determined using aMalvern Mastersizer 2000 with the Hydro-S dispersion unit in water. Themeasurement was performed according to ISO 13320:2009 using theFraunhofer method for the analysis.

COMPARATIVE EXAMPLE 1 Synthesis According to Example 27 of EP 1172139 B1

Composition: 61.5% Al₂O₃, 21% CeO₂, 15% ZrO₂, 2.5% Y₂O₃

A mixture consisting of 96.43 g of an aqueous solution of zirconylnitrate (ZrO₂ content=7%), 52.5 g of an aqueous solution of cerium(III)nitrate (CeO₂ content=18%), 6.32 g of an aqueous solution of yttriumnitrate (Y₂O₃ content=17.80%) and 205.61 g aluminum nitrate nonahydratein crystalline form was mixed with 600 mL water and stirred untilobtaining a clear solution.

This solution was mixed with 7.47 g of a 35% H₂O₂ solution(corresponding to 1.2 times the molar quantity of cerium) and thismixture was stirred for approx. 25 minutes. The resulting solution wasthen brought to a pH of 7 by adding a 24% ammonia solution and stirredfor 15 minutes. The resulting mixture was filtered and the filterresidue was washed with deionized water at 60° C. This filter cake wasthen dried at 120° C. for sixteen hours. Following that, the dry filtercake was calcined first at 300° C. for five hours and then at 700° C.for five hours.

The measured surface area is shown in Table 1.

BET after 300° C./5 hours+700° C./five hours (starting material): 168m²/g

BET after 950° C./5 hours: 109 m²/g

BET after 1000° C./4 hours: 84 m²/g

BET after 1100° C./2 hours: 32 m²/g

COMPARATIVE EXAMPLE 2 Synthesis According to Example 1 of EP 1172139 B1Composition: 41% Al₂O₃, 30% CeO₂, 23% ZrO₂, 2.5% Y₂O₃, 3.5% La₂O₃

A mixture consisting 145.93 g of an aqueous solution of zirconyl nitrate(ZrO₂ content=7%), 72.25 g of an aqueous solution of cerium(III) nitrate(CeO₂ content=18%), 6.07 g of an aqueous solution of yttrium nitrate(Y₂O₃ content=17.80%), 10.81 g of an aqueous solution of lanthanumnitrate (La₂O₃ content=14.57%) and 138.08 g aluminum nitrate nonahydratein crystalline form was mixed with 600 mL water and stirred until aclear solution was obtained.

This solution was mixed with 10.71 g of a 35% H₂O₂ solution(corresponding to 1.2 times the molar quantity of cerium) and thismixture was stirred for approx. 25 minutes. The resulting solution wasthen brought to a pH of 7 by adding a 24% ammonia solution and stirredfor 15 minutes. The resulting mixture was filtered and the filterresidue was washed with deionized water at 60° C.

This filter cake was then dried at 120° C. for sixteen hours. Followingthat, the dry filter cake was calcined first at 300° C. for five hoursand then at 700° C. for five hours.

The measured surface area is shown in Table 2.

COMPARATIVE EXAMPLE 3 Synthesis According to Example 6 of WO 2006/070201A2 Composition: 51% Al₂O₃, 14.2% CeO₂, 34.8% ZrO₂

An aluminum nitrate solution was prepared by stirring 112.5 g aluminumnitrate monohydrate into 1500 mL water. To this solution were added14.77 g of a cerium(III) nitrate solution (CeO₂ content=28.85%) and149.16 [g] of a zirconyl nitrate solution (ZrO₂ content=7%). Thismixture was then stirred at room temperature for 15 minutes. A pH of 10was adjusted by adding 25% sodium hydroxide solution and this value wasmaintained during the precipitation process. Then 5 g of 35% H₂O₂solution was added and the pH was again adjusted to 10. The resultingsuspension was then stirred for 60 minutes. Following that the pH wasset at 8 by adding 30% nitric acid and the suspension was again stirredfor 30 minutes.

The resulting mixture was filtered and the filter residue was washedwith deionized water at 60° C. This filter cake was then suspended in850 mL deionized water and the pH was adjusted to 10 by adding 25%sodium hydroxide solution. The mixture was then autoclaved for six hoursat 120° C. The aged suspension was cooled to room temperature, adjustedto a pH of 8 by adding nitric acid and then stirred for 30 minutes.

Following that the suspension was again stirred for one hour at 60° C.and then the liquid was filtered. The resulting filter cake was thenwashed with deionized water at 60° C. and following that calcined for 4hour at 850° C. The measured surface area is given in Table 3.

COMPARATIVE EXAMPLE 4 Synthesis According to Example 12 of WO2012/067654 A1 Composition: 50% Al₂O₃, 30% CeO₂, 15% ZrO₂, 3.5% La₂O₃,1.5% Y₂O₃

Solution A was prepared by adding 6.0 g of a solution of lanthanumnitrate (La₂O₃ content 14.57%) to 53 g of a 24% ammonia solution and 110g distilled water.

Solution B was prepared by combining 22.19 g zirconyl nitrate (ZrO₂content=33.80%), 35.89 g cerium(III) nitrate (CeO₂ content=41.80%), 4.21g of a solution of yttrium nitrate (Y₂O₃ content=4.21%), 100 g distilledwater and hydrogen peroxide with a molar ratio of H₂O₂/CeO₂ of 3.

Solution C was prepared by the dissolving 46.3 g sodium aluminate in 200g distilled water.

Starting with 2 liters of distilled water, it was heated to 65° C.Solution A was added by drops within 25 minutes and the pH was kept at7.3 at the same time by adding solution C. After adding all of solutionA, the remainder of solution C was added completely, thereby adjustingthe pH to 9.8. Next the resulting suspension was adjusted to a pH of 4using dilute nitric acid. Following that solution B was added within 20minutes. Meanwhile the pH was kept at 4 by adding 10% ammonia solution.After completely adding solution B the pH was raised to 8.2 by addingconcentrated ammonia solution. The suspension was filtered and thesolids were washed with 2 liters of an aqueous solution of ammoniumbicarbonate (120 g/liter H₂O) heated to 60° C. Table 4 lists theresulting surface areas.

COMPARATIVE EXAMPLE 5 Synthesis According to Comparative Example 3 ofU.S. Pat. No. 6,831,036 and/or Example 7 of WO 2006/119549 A1Composition: 50% Al₂O₃, 30% CeO₂, 15% ZrO₂, 3.5% La₂O₃, 1.5% Y₂O₃

15 g CeO₂, 7.5 g ZrO₂, 1.75 g La₂O₃ and 0.75 g and 0.75 g Y₂O₃ in theform of their nitrates were dissolved in water, then 31.53 g DISPERAL HP14 (boehmite Al₂O₃ content=79.3%) was added to this acidic solution andthe resulting suspension was stirred for 30 minutes. Concentratedammonia solution (300 g) was diluted with 750 mL water and used as thestarting material at room temperature. The acidic boehmite/metal nitratesolution was added by drops slowly to the ammonia solution and stirringwas continued for 30 minutes after the addition was concluded. Thesolids were separated by filtration, washed with 1.5 liters water andthen dried for sixteen hours at 100° C.

Table 4 shows the resulting surface areas.

EXAMPLE A1 Preparing an Alkaline Boehmite Suspension by Using a PureBoehmite

A suspension with an Al₂O₃ content of 5% was prepared by stirringDISPERAL HP 14 (boehmite) into deionized water at pH 7. Next the pH wasset at 10 by adding a 24% ammonia solution. The particle sizes in thesuspension were determined by laser diffraction (Mastersizer):

D₁₀=0.96 μm; D₅₀=5.11 μm; D₉₀=28.34 μm

The measured particle size distributions are shown in FIG. 1.

EXAMPLE A2 Preparing an Alkaline Boehmite Suspension by Using a ModifiedBoehmite

A suspension with an Al₂O₃ content of 5% was prepared by stirringDISPERAL HP 14/7 (boehmite modified with citric acid) into deionizedwater at pH 7. Next the pH was set at 10 by adding a 24% ammoniasolution. The particle sizes in the suspension were determined by laserdiffraction (Mastersizer):

D₁₀=0.09 μm; D₅₀=0.23 μm; D₉₀=0.67 μm

The measured particle size distributions are shown in FIG. 1.

EXAMPLE 1 (ACCORDING TO THE INVENTION) Composition: 61.5% Al₂O₃, 21%CeO₂, 15% ZrO₂, 2.5% Y₂O₃ Corresponds to Comparative Example 1

A metal salt solution consisting of 81.4 g of a solution of ammoniumcerium(IV) nitrate (CeO₂ content =12.90%), 103.30 g of a solution ofzirconyl nitrate (ZrO₂ content=7.26%) and 7.0 g of a solution of yttriumnitrate (Y₂O₃ content=17.80%) was used as the starting material whichwas heated to 90° C.

A suspension consisting of 615.0 g DISPERAL HP 14/7 (boehmite modifiedwith citric acid) (Al₂O₃ content=5%) was prepared by stirring the solidsinto deionized water and then adding 24% ammonia solution up to a pH of10. The suspension was added by drops slowly to the metal salt solutionand after the addition was completed the pH was adjusted to 8.7 byadding 24% ammonia solution. This mixture was then stirred for 30minutes at 90° C. Following that the mixture was filtered and the filterresidue was washed with deionized water at 60° C. The filter cake wasresuspended in deionized water while stirring and was then spray dried(inlet temperature=220° C., outlet temperature=110° C.). The driedmaterial was calcined for four hours at 850° C.

EXAMPLE 2 (ACCORDING TO THE INVENTION) Composition: 41% Al₂O₃, 30% CeO₂,23% ZrO₂, 2.5% Y₂O₃, 3.5% La₂O₃ Corresponds to Comparative Example 2

A metal salt solution consisting of 96.9 g of a solution of ammoniumcerium(IV) nitrate (CeO₂ content=12.90%), 131.96 g of a solution ofzirconyl nitrate (ZrO₂ content=7.26%), 10.02 g of a solution oflanthanum nitrate (La₂O₃ content=14.57%) and 5.84 g of a solution ofyttrium nitrate (Y₂O₃ content=17.80%) was used as the starting materialwhich was heated to 90° C. A suspension consisting of 341.6 g DISPERALHP 14/7 (boehmite modified with citric acid) (Al₂O₃ content=5%) wasprepared by stirring the solids into deionized water and then adding 24%ammonia solution up to a pH of 10.

TABLE 1 Measured BET surface areas from Comparative Example 1 andExample 1 after calcining (m²/g). Comparative Example 1 Example 1 (likeEP 1 172 139) (acc. to invention) 5 h/300° C. + 5 h/700° C. 168 126(starting material) 5 h/950° C. 109 95 4 h/1000° C. 84 89 2 h/1100° C.32 70

The suspension was added by drops slowly to the metal salt solution andafter the addition was completed the pH was adjusted to 8.5 by adding24% ammonia solution. This mixture was then stirred for 30 minutes at90° C. Following that the mixture was filtered and the filter residuewas washed with deionized water at 60° C. The filter cake wasresuspended in deionized water while stirring and was then spray dried(inlet temperature=220° C., outlet temperature=110° C.). The driedmaterial was calcined for four hours at 850° C.

In FIG. 2 the x-ray powder diffractograms of the material from Example 2after calcining are shown

a) after calcining 4 h at 850° C.

b) after calcining 4 h at 850° C.+4 h at 1100° C.

c) after calcining 4 h at 850° C.+24 h at 1100° C.

d) simulated diffractogram of CeO₂ (cubic)

e) simulated diffractogram of CeO₂ (tetragonal)

EXAMPLE 3 (ACCORDING TO THE INVENTION) The Composition CorrespondsExactly to that from Comparative Example 2 41% Al₂O₃, 30% CeO₂, 23%ZrO₂, 2.5% Y₂O₃, 3.5% La₂O₃

220.4 g of a suspension of Pural SB (boehmite, Al₂O₃ content=9.3%) (pH9.5) was adjusted to a pH of 9.5 with a 24% ammonia solution and used asthe starting material. At room temperature, a mixture consisting of 300g of a solution of cerium acetate (CeO₂ content=5.0%), 50.3 g of asolution of zirconium acetate (ZrO₂ content=22.88%), 24.0 g of asolution of lanthanum acetate (La₂O₃ content=7.3%) and 31.3 g of asolution of yttrium acetate (Y₂O₃ content=4.0%) was added slowly at roomtemperature. The pH value was kept constant at 9.5 by adding a 24%ammonia solution at the same time. The resulting mixture was thenstirred for 45 minutes. Next the suspension was autoclaved for threehours at 140° C. The resulting mixture was filtered and the solids werewashed with deionized water at 60° C. This filter cake was dried forsixteen hours in a drying cabinet and then calcined at 850° C.

EXAMPLE 4 (ACCORDING TO THE INVENTION) Composition: 41% Al₂O₃, 30% CeO₂,23% ZrO₂, 2.5% Y₂O₃, 3.5% La₂O₃ Corresponds to Comparative Example 2

A boehmite suspension consisting of 492.0 g DISPERAL HP 14/7 (boehmitemodified with citric acid) (Al₂O₃ content=5%) was prepared by stirringthe solids into deionized water and then adding 24% ammonia solution upto a pH of 10.

At 90° C. a metal salt solution consisting of 139.53 g of a solution ofammonium cerium(IV) nitrate (CeO₂ content=12.90%), 190.1 g of a solutionof zirconyl nitrate (ZrO₂ content 7.26%), 14.41 g of a solution oflanthanum nitrate (La₂O₃ content 14.57%) and 5.45 g of a solution ofyttrium acetate (Y₂O₃ content 27.54%) was added slowly by drops to thissuspension. The pH value was kept constant at 9.0 by adding a 24%ammonia solution at the same time. This mixture was then stirred for 30minutes at 90° C. Following that the mixture was filtered and the filterresidue was washed with deionized water at 60° C. The filter cake wasresuspended in deionized water while stirring and then spray dried(inlet temperature=220° C., outlet temperature=110° C.). The driedmaterial was calcined for four hours at 850° C.

EXAMPLE 5 Composition: 41% Al₂O₃, 30% CeO₂, 23% ZrO₂, 2.5% Y₂O₃, 3.5%La₂O₃ Corresponds to Comparative Example 2 but Using by Cerium(III)Nitrate+H₂O₂

A metal salt solution consisting of 58.34 g of a solution of cerium(III)nitrate (CeO₂ content=18.00%), 131.96 g of a solution of zirconylnitrate (ZrO₂ content=7.26%), 10.02 g of a solution of lanthanum nitrate(La₂O₃ content=14.57%) and 5.84 g of a solution of yttrium acetate (Y₂O₃content 17.80%) was used as the starting material.

At room temperature 25.74 g of a 30% H₂O₂ solution cooled to 5° C. wasadded. The resulting suspension was stirred for 10 minutes and thenheated to 90° C. A suspension consisting of 341.6 g DISPERAL HP 14/7(boehmite modified with citric acid) (Al₂O₃ content 5%) was adjusted toa pH of 10 by stirring the solids into deionized water and then adding a24% ammonia solution.

The suspension was added by drops slowly to the metal salt solution andafter the addition was completed the pH was adjusted to 8.3 by adding24% ammonia solution. This mixture was then stirred for 30 minutes at90° C. Following that the mixture was filtered and the filter residuewas washed with deionized water at 60° C. The filter cake wasresuspended in deionized water while stirring and was then spray dried(inlet temperature=220° C., outlet temperature=110° C.). The driedmaterial was calcined for four hours at 850° C.

TABLE 2 Measured surface areas (BET) from Examples 2-6 and ComparativeExample 2 after calcining in m²/g. Comparative Exam- Exam- Exam- Exam-Example 2, like ple 2 ple 3 ple 4 ple 5 EP 1 172 139 According to theinvention 4 h/850° C. 112 98 89 88 85 (starting material)  4 h/1100° C.18 49 34 46 51 24 h/1100° C. 12 45 34 39 37 36 h/1150° C. 20 25  4h/1200° C. 16 21

EXAMPLE 6 (ACCORDING TO THE INVENTION) Composition: 51% Al₂O₃, 14.2%CeO₂, 34.8% ZrO₂ Corresponds to Comparative Example 3

A metal salt solution consisting of 55.0 g of a solution of ammoniumcerium(IV) nitrate (CeO₂ content 12.90%) and 239.7 g of a solution ofzirconyl nitrate (ZrO₂ content 7.26%) was used as the starting materialand heated to 90° C.

A suspension consisting of 510.0 g DISPERAL HP 14/7 (boehmite modifiedwith citric acid) (Al₂O₃ content 5%) was adjusted to a pH of 10 bystirring the solids into deionized water and then adding a 24% ammoniasolution.

This suspension was added by drops slowly to the metal salt solution andafter the addition was completed the pH was adjusted to 8.7 by adding24% ammonia solution. This mixture was then stirred for 30 minutes at90° C. Following that the mixture was filtered and the filter residuewas washed with deionized water at 60° C. The filter cake wasresuspended in deionized water while stirring and was then spray dried(inlet temperature=220° C., outlet temperature=110° C.). The driedmaterial was calcined for four hours at 850° C.

The values from Comparative Example 3 are given in parentheses.

BET after 850° C./4 hours (starting material): 97 m²/g (107)

BET after 1100° C./2 hours: 62 m²/g (47)

BET after 1100° C./24 hours: 36 m²/g (35)

TABLE 3 Measured surface areas (BET) from Comparative Example 3 andExample 7 after calcining (m²/g). Comparative Example 3 Example 6 (likeWO 2006/070201) (according to the invention) 850° C./4 hours 107 97(starting material)  2 h/1100° C. 47 62 24 h/1100° C. 35 36

EXAMPLE 7 (ACCORDING TO THE INVENTION) Composition: 50% Al₂O₃, 30% CeO₂,15% ZrO₂, 3.5% La₂O₃, 1.5% Y₂O₃ Corresponds to Comparative Examples 4and 5

A metal salt solution consisting of 116.3 g of a solution of ammoniumcerium(IV) nitrate (CeO₂ content=12.90%), 103.3 g of a solution ofzirconyl nitrate (ZrO₂ content=7.26%), 12.1 g of a solution of lanthanumnitrate (La₂O₃ content=14.50%) and 4.2 g of a solution of yttriumacetate (Y₂O₃ content=17.80%) and heated to 90° C.

A suspension consisting of 500 g DISPERAL HP 14/7 (boehmite modifiedwith citric acid) (Al₂O₃ content 5%) was adjusted to a pH of 10 bystirring the solids into deionized water and then adding a 24% ammoniasolution.

This suspension was added by drops slowly to the metal salt solution andafter the addition was completed the pH was adjusted to 8.3 by adding24% ammonia solution. This mixture was then stirred for 30 minutes at90° C. Following that the mixture was filtered and the filter residuewas washed with deionized water at 60° C. The filter cake was dried forsixteen hours at 120° C. and then calcined for four hours at 850° C.

EXAMPLE 8 (ACCORDING TO THE INVENTION) Composition: 50% Al₂O₃, 30% CeO₂,15% ZrO₂, 3.5% La₂O₃, 1.5% Y₂O₃ Corresponds to Comparative Examples 4and 5

A metal salt solution consisting of 116.3 g of a solution of ammoniumcerium(IV) nitrate (CeO₂ content=12.90%), 103.3 g of a solution ofzirconyl nitrate (ZrO₂ content=7.26%), 12.1 g of a solution of lanthanumnitrate (La₂O₃ content=14.50%) and 4.2 g of a solution of yttriumacetate (Y₂O₃ content=17.80%) and heated to 90° C.

A suspension consisting of 500 g DISPERAL HP 14/7 (boehmite modifiedwith citric acid) (Al₂O₃ content=5%) was adjusted to a pH of 10 bystirring the solids into deionized water and then adding a 24% ammoniasolution. This suspension was added by drops slowly to the metal saltsolution and after the addition was completed the pH was adjusted to 9.0by adding 24% ammonia solution. This mixture was then stirred for 30minutes at 90° C. Following that the mixture was filtered and the filterresidue was washed with deionized water at 60° C. The filter cake wasresuspended in deionized water while stirring and was then spray dried(inlet temperature=220° C., outlet temperature=110° C.). The driedmaterial was calcined for four hours at 850° C.

EXAMPLE 9 (ACCORDING TO THE INVENTION) Composition: 70% Al₂O₃, 20% CeO₂,7% ZrO₂, 3.0% La₂O₃

A boehmite suspension consisting of 420.0 g DISPERAL HP 14/7 (boehmitemodified with citric acid) (Al₂O₃ content=5%) was adjusted to a pH of 10by stirring the solids into deionized water and then adding a 24%ammonia solution. At 90° C. a metal salt solution consisting of 46.51 gof a solution of ammonium cerium(IV) nitrate (CeO₂ content=12.9%), 30.0g of a solution of zirconyl nitrate (ZrO₂ content=7.0%) and 6.18 g of asolution of lanthanum nitrate (La₂O₃ content=14.57%) was added by dropsslowly to this suspension. The pH was kept constant at 9.0 by adding a24% ammonia solution at the same time. This mixture was then stirred for30 minutes at 90° C. Following that the mixture was filtered and thefilter residue was washed with deionized water at 60° C. The filter cakewas resuspended in deionized water while stirring and then dried forsixteen hours at 120° C. The dried material was next calcined at 850° C.

TABLE 4 Measured surface areas (BET) from Comparative Examples 4 and 5and Examples 8-10 in m²/g. Comparative Comparative Example 4 Calculated*Example 5 Example 7 Example 8 Example 9 4 h/850° C. 130 — 96 92 96 101(starting material) 4 h/1200° C. 17 22 (5 h) 23 23 25 40 *Surface areascalculated on the basis of the formulas given in WO2012/067654 A1

1-13. (canceled)
 14. An Al/Ce/Zr oxide composite comprising aluminumoxide and cerium/zirconium mixed oxides in the form of a “solidsolution”, wherein Al₂O₃ and the Ce/Zr and optionally rare earth (RE)mixed oxides are homogeneously distributed side by side comprising 20%to 80% by weight aluminum, calculated as Al₂O₃; 5% to 80% by weightzirconium, calculated as ZrO₂; 5% to 80% by weight cerium, calculated asCeO₂; and 0% to 12% by weight, rare earth metal(s) (RE) calculated asRE₂O₃.
 15. The oxide composite according to claim 14 comprising 0.1% to9% by weight, rare earth metal(s) (RE), calculated as RE₂O₃.
 16. Theoxide composite according to claim 14 comprising 40% to 70% by weight,aluminum, calculated as Al₂O₃; 5% to 40% by weight, zirconium,calculated as ZrO₂; 5% to 40% by weight, cerium, calculated as CeO₂; and0 to 12% by weight, rare earth metal(s) (RE), calculated as RE₂O₃. 17.The oxide composite according to claim 14 having after 4 h at 1200° C. asurface area of at least 20 m²/g.
 18. The oxide composite according toclaim 14 having after 4 h at 1200° C. a surface area of at least 40m²/g.
 19. The composite according to claim 14, wherein the oxidecomposite is an Al/Ce/Zr rare earth oxide composite comprising as rareearth oxides the oxides of neodymium, praseodymium, yttrium and/orlanthanum.
 20. The composite according to claim 14 further comprisingplatinum, rhodium and/or palladium.
 21. The composite according to claim14, wherein the composite aluminum oxide and cerium/zirconium andoptionally rare earth mixed oxides are obtained by a method comprisingthe following steps: (a) providing a suspension comprising boehmite asthe alumina precursor and adjusting the pH to 6 to 11.5; (b) providingan aqueous metal salt solution comprising at least metal salts of ceriumand of zirconium; (c) bringing the suspension of (a) in contact with themetal salt solution from (b) at temperatures of 5 to 95° C. orsubjecting the slurry so obtained to a temperature of from 5 to 95° C.;(d) isolating the solids from (c) and (e) calcining the solids from (d).22. The composite according to claim 21, wherein i) the boehmites areadded having at least one carboxyl group (—COO and/or —COOH) and one ormore further groups selected from hydroxy (—OH), oxo (—O), carboxy (—COOand/or —COOH) and/or amine (—NH and/or —NH₂) groups; or ii) thesuspension of step (c) is hydrothermally aged in an aqueous environment,at a temperature of at least 90° C. and for at least one hour, or iii)the measures according to i) and ii) both are applied.
 23. The compositeaccording to claim 21, wherein the composite also comprises one or moremembers of the following group: alkaline earth elements/compounds, rareearth elements/compounds, zirconium compounds and silicon compounds,which are water soluble and which are added before drying or only afterstep (c) or even after (d).
 24. The composite according to claim 21,wherein, wherein the suspension of (c) is hydrothermally aged in anaqueous environment at a temperature of at least 120° C. for at leastfour hours.
 25. The composite according to claim 21, wherein thewater-soluble metal salts are acetates, nitrates and/or chlorides. 26.The composite according to claim 21, wherein no alkali and/or alkalineearth salts are added, except for barium salts.
 27. The compositeaccording to claim 21, wherein the suspension comprising boehmite isadjusted to the pH by a nitrogen base.